CN101325980B - Silver ion releasing articles and methods of manufacture - Google Patents
Silver ion releasing articles and methods of manufacture Download PDFInfo
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- CN101325980B CN101325980B CN200680045936XA CN200680045936A CN101325980B CN 101325980 B CN101325980 B CN 101325980B CN 200680045936X A CN200680045936X A CN 200680045936XA CN 200680045936 A CN200680045936 A CN 200680045936A CN 101325980 B CN101325980 B CN 101325980B
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
- A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
- A61L2300/104—Silver, e.g. silver sulfadiazine
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
- A61L2300/602—Type of release, e.g. controlled, sustained, slow
Abstract
A biologically-active article includes a substrate having a substrate surface and a silver releasing chromonic material disposed adjacent to the substrate surface. The silver releasing chromonic material includes a chromonic compound and a silver ion source. Methods of forming the same are also disclosed.
Description
Background technology
The disclosure relates to silver ion releasing articles.More particularly, the disclosure relates to the method that colour product and these goods of preparation are arranged that discharges silver ion.
Silver is well-known because of its antimicrobial acivity.Greek and Roman use the container of silver-colored lining to come purified water.Used the antimicrobial treatment of silver nitrate before more than 100 year as burn wound.Nineteen sixties, silver-colored sulfadiazine cream replaces the antimicrobial treatment of silver nitrate as burn wound.The antimicrobial effect that it is believed that silver at least partly is owing to free silver ions or money base, and wherein silver ion prevents that through sticking to it from duplicating through blocking-up Cellular respiration approach on the cell DNA, and comes kill microorganisms through destroying cell membrane.
It is believed that wound heals better in moistening environment.Yet, keep the moistening bacterial multiplication that causes on the wound surface of wound.A method that prevents wound infection is through using antibiotic.Yet owing to produce the problem of antibiotic-resistant antibacterial, suggesting system for wearing does not use antibiosis usually to prevent wound infection.Many silver compounds such as silver nitrate, are prone to dissolve in moistening environment very much, and oxidation rapidly, thereby make dyschromasia that the antimicrobial acivity of short time also only is provided.The antimicrobial wound dressing that needs a kind of wide spectrum to continue to discharge is used to handle chronic wounds.
Summary of the invention
The disclosure provides silver-colored delivery article, relates to specifically discharging colour product being arranged and preparing its method of silver ion.In certain embodiments, these colour products that have that discharge silver ions provide the sustained release of the silver ion of time dependence, even under moistening condition.
An aspect of the present disclosure relates to a kind of biological activity goods, and it comprises that substrate with substrate surface and the silver that contiguous said substrate surface is provided with discharge colored materials.Silver discharges colored materials and comprises colored compound and source of silver ions.
Aspect another, the method that forms silver-colored delivery article has been described of the present disclosure.These methods comprise: the substrate with substrate surface is provided; Silver salt and colored compound are combined to form aqueous silver colored solutions in aqueous solution; Contiguous said substrate surface is provided with said silver-colored colored solutions and forms the substrate that is coated; From the substrate that is coated, remove then and anhydrate, to form the nonferrous layer that discharges silver ion.
Top summary of the invention is not intended to describe each disclosed embodiment of the present disclosure or each practical implementation.Accompanying drawing subsequently, the specific embodiment and instance more specifically exemplary illustration these embodiment.
Description of drawings
Hereinafter to the specific descriptions of various embodiment, can understand the disclosure more fully in conjunction with the drawings, wherein:
Fig. 1 is the schematic cross sectional views of exemplary wound dressing goods.
The present invention has various changes and alternative form, and its details has illustrated through the example in the accompanying drawing and will elaborate.Yet should be appreciated that the present invention is not limited to described specific embodiment.On the contrary, the objective of the invention is to cover all modifications, equivalent and the alternative form that belongs in the spirit and scope of the present invention.
The specific embodiment
The disclosure provides silver-colored delivery article, relates to specifically discharging colour product being arranged and preparing its method of silver ion.In certain embodiments, these colour products that have that discharge silver ions provide the sustained release of the silver ion of time dependence, even under moistening condition.
For the following term definition that provides, its purpose is to be as the criterion with these definition, only if in claim or provided different definition in this manual in addition.
Percentage by weight, percentages, by weight percentage, %wt etc. is synonym, the concentration that is meant material multiply by 100 for the weight of this material divided by the weight of said compositions then.
Numerical range by the end points statement comprises all numerical value (for example, 1 to 5 comprises 1,1.5,2,2.75,3,3.80,4 and 5) that are included in this scope.
Only if clearly point out in addition in the literary composition, such as in this description and the accompanying claims use, singulative " a kind of " and " said " comprise the plural number things.Therefore, for example, mention that the compositions that comprises " layer " comprises two or more layers.Such as in this description and the additional claim use, term " or " generally with comprise " and/or " the meaning use, only if in have in addition clearly statement.
Should understand, except as otherwise noted, be expressed as the numeral that dosis refracta, characteristic are measured etc. in this description that is useful on and the claim, all can be modified in all instances by term " about ".Therefore, only if opposite indication is arranged, the numerical parameter described in above-mentioned description and the accessory claim is an approximation, and according to the desirable characteristics that uses the present invention to instruct those skilled in the art of content to be intended to reach, this numerical parameter can change.At least, not with the application limitations of doctrine of equivalents the meaning, should and use the usual technology of rounding off to explain each numerical parameter according to the number of the significant digits of being reported at least in the scope of claim protection.Though numerical range and the parameter of setting forth broad scope of the present invention are approximations, numerical value listed in specific embodiment is then as far as possible by accurately report.Yet any numerical value must comprise certain error, and these errors must cause owing to existing standard deviation in the thermometrically separately.
Term " colored materials " (or " colored compound ") is meant big, multi-ring molecule, its typical characteristic be to exist by the hydrophobic core of a plurality of hydrophobic (referring to, for example; Attwood; T.K. and Lydon, " the Molec.Crystals Liq.Crystals " 108,349 (1984) of J.E.).Said hydrophobic core can comprise aromatic ring and/or non-virtue property ring.When in solution, these colored materials are tending towards being gathered into the nematic ordering, and it characterizes through long-range order.In the time of in being dissolved in aqueous solution (preferred alkaline aqueous solution), colored materials can be formed with form and aspect or assembly.It is known that form and aspect or assembly are arranged, and is made up of plane, the range upon range of of polycyclic aromatic molecule.Said molecule has constituted the hydrophobic core that is centered on by hydrophilic group.The range upon range of variform of taking, but characterize through the tendency of formation usually by the post of the range upon range of generation of layer.The ordered molecular of growth is range upon range of along with the concentration increase in formation.
The distinct layer stack structure of coloured molecule makes the silver ion in the aqueous solution to stablize.These solution can be sent with various methods, comprise coating, dipping and non-contacting deposition process, like spraying and ink jet printing.In addition, the antimicrobial silver ion of coloured molecule may command is discharged into the speed in the wound, thereby provides lasting silver ion to discharge.
Fig. 1 is the schematic cross sectional views of exemplary wound dressing goods 100.Illustrated layer is not in scale.These goods 100 comprise the colored materials 120 of substrate 110 with substrate surface 112 and the release silver ion that is close to substrate surface 112 settings.The colored materials 120 that discharges silver ion comprises colored compound and source of silver ions 122.In certain embodiments, adhesive phase 130 is arranged on substrate 110 and discharges between the colored materials 120 of silver ion.
Use colored materials to encapsulate source of silver ions, and the sustained release of silver ion from coloured structure is provided.In many examples, the release of silver ion triggers and controls through coloured structure is exposed to moist environment.Do not receive the constraint of any particular theory, it is believed that the plane aromatic structure in the coloured molecule has produced self-assembled structures, its straight line is formed the direction laminated that is incorporated in perpendicular to straight line association direction.These associations can cause into the hole of row, and source of silver ions can be inserted wherein.
The colored materials 120 that discharges silver ion can any available mode form.In many examples, source of silver ions and colored compound are combined to form the colored materials that discharges silver ion in aqueous solution.These colored materials that discharge silver ion can be represented with one of following universal architecture:
Wherein, Each R
2Be independently selected from the group of forming by following: electron-donating group, electron withdraw group and electric neutrality group; R
3Be selected from the group of being made up of following: replace and unsubstituted hetero-aromatic ring and replacement and unsubstituted heterocycle, these rings pass through R
3Intra-annular nitrogen-atoms is connected on the triazine group, and M
+Be the silver metal cation.R preferably
3Be selected from the group of forming by following replacement and unsubstituted hetero-aromatic ring.
Above-mentioned universal architecture has shown following orientation, and wherein carboxyl is para-position (Formula I) with respect to the amino that is connected on the chemical compound triazine main chain, and wherein carboxyl with respect to be connected to amino on the triazine main chain be between position (Formulae II).Carboxyl also can be the combination of a para-position and a position orientation (not shown).In certain embodiments, be oriented to para-position.
In many examples, each R
2Be hydrogen or replacement or unsubstituted alkyl.In certain embodiments, R
2Be independently selected from the group of forming by following: hydrogen, unsubstituted alkyl, by hydroxyl or the substituted alkyl of halogenated functional group, and the alkyl that comprises ether, ester or sulfonyl.In one embodiment, R
2Be hydrogen.
R
3Can be, but be not limited to, derived from the hetero-aromatic ring of pyridine, pyridazine, pyrimidine, pyrazine, imidazoles 、 oxazole 、 isoxazole thiazole 、 oxadiazole, thiadiazoles, pyrazoles, triazole, triazine, quinoline and isoquinolin.In many examples, R
3Comprise hetero-aromatic ring derived from pyridine or imidazoles.Hetero-aromatic ring R
3Substituent group can be selected from, but be not limited to the group of forming by replacement and unsubstituted alkyl, carboxyl, amino, alkoxyl, sulfo-, cyanic acid, amide, sulfonyl, hydroxyl, halogenide, perfluoroalkyl, aryl, ether and ester.In certain embodiments, R
3Substituent group be selected from the group of forming by following: alkyl, sulfonyl, carboxyl, halogenide, perfluoroalkyl, aryl, ether, and by the substituted alkyl of hydroxyl, sulfonyl, carboxyl, halogenide, perfluoroalkyl, aryl or ether.Work as R
3During for substituted pyridine, said substituent group is preferably placed at 4.Work as R
3During for substituted imidazoles, said substituent group is preferably placed at 3.
R
3Representative example comprise below shown in 4-(dimethylamino) pyridine-1-base, 3-Methylimidazole .-1-base, 4-(pyrrolidine-1-yl) pyridine-1-base, 4-isopropyl pyridine-1-base, 4-[(2-ethoxy) methylamino] pyridine-1-base, 4-(3-hydroxypropyl) pyridine-1-base, 4-picoline-1-base, quinoline-1-base, 4-tert .-butylpyridine-1-base and 4-(2-sulfoethyl) pyridine-1-basic.
R
3Also available following universal architecture is represented:
R wherein
4Be hydrogen or replacement or unsubstituted alkyl.In many examples, R
4Be selected from the group of forming by following: hydrogen, unsubstituted alkyl, and by the substituted alkyl of hydroxyl, ether, ester, sulphonic acid ester or halide functional group.In many examples, R
4Be selected from the group of forming by following: sulfonic acid propyl group, methyl and oleyl.
R
3Also can be selected from the substituted heterocycle of N-, for example, morpholine, pyrrolidine, piperidines and piperazine.
In many examples, colored compound can be represented with one of following structure:
X wherein
-Be counter ion counterionsl gegenions.In certain embodiments, X
-Be selected from the group of forming by following: HSO
4 -, Cl
-, CH
3COO
-And CF
3COO
-
Formula I V has described to be in the chemical compound of its zwitterionic form.Therefore pyridine nitrogen is positively charged, and the electronegative (COO of carboxyl functional group
-).
For example, the colored materials of release silver ion can begin to prepare through coloured initial compounds of representing with one of following structure:
R wherein
2With above-mentioned identical.
Like United States Patent(USP) No. 5,948, the prepare that 487 people such as () Sahouani (document is incorporated herein said in full with way of reference), the pyrrolotriazine derivatives such as the coloured initial compounds with chemical formula V can aqueous solutions.A kind of synthetic route of the triazine molecule shown in the above-mentioned chemical formula V relates to two step process.With 4-aminobenzoic acid treatment cyanuric chloride, obtain 4-{ [4-(4-carboxyl anilino-)-6-chloro-1,3,5-triazines-2-yl] amino } benzoic acid.This intermediate is handled with replacement or unsubstituted nitrogen heterocyclic ring.Assorted ring nitrogen replaces the chlorine atom on the triazine, forms corresponding chlorinated thing salt.The preparation of zwitterionic derivative can make it through anion-exchange column chloride replaced with hydroxide downwards through chloride salt is dissolved in the ammonium hydroxide then, and (making the protonated generation amphion of carboxylic acid) removed then and desolvated.Another kind of alternative structure shown in above-mentioned chemical formula VI, can obtain through using 3-amino benzoic Acid rather than 4-amino benzoic Acid.
These coloured initial compounds can for example at room temperature place aqueous solution.Usually, add said coloured initial compounds in about 5 weight % to 20 weight % (or the about 10 weight %) scope that obtains said solution in the solution concentration.Coloured initial compounds in the solution can mix with excessive source of silver ions then.
Suitable source of silver ions instance comprises, for example, and silver oxide, silver sulfate, silver acetate, silver chloride, actol, silver phosphate, silver stearate, silver thiocyanate, argyrol salt, Disilver carbonate, silver nitrate, silver-colored sulfadiazine, alginic acid silver, and their combination.In many examples, source of silver ions comprises silver salt, for example, and Disilver carbonate, silver nitrate and silver acetate.In certain embodiments, source of silver ions is water soluble silver salt, for example silver nitrate.The dissolubility of silver salt can improve through adding ammonia or ammonium salt, and this is known in the art.
In the silver colored solutions instance of the suitable concn of source of silver ions based on the gross weight of said silver-colored colored solutions about 0.1 weight % to the scope of about 15 weight %.In certain embodiments, in the silver-colored colored solutions concentration of source of silver ions based on the gross weight of said silver-colored colored solutions about 1 weight % to the scope of about 5 weight %.
About silver oxide, can use silver oxide multiple valent state (as, oxidation state is silver oxide (II) or silver oxide (III) situation).The valent state of silver oxide can be through the given valent state of deposition silver oxide (like, Ag
2O, AgO, Ag
2O
3, Ag
2O
4) confirm.As other a kind of selection, the valent state of silver oxide can be through adding oxidant in silver-colored colored solutions, or oxidant is applied on the nonferrous layer 120 after being applied to silver-colored colored solutions on the goods 100 again and increases.Suitable oxidant instance comprises hydrogen peroxide, alkali metal persulphate, permanganate, hypochlorite, perchlorate, nitric acid, and their combination.Suitable alkali metal persulphate instance comprises sodium peroxydisulfate, and like the United States Patent (USP) 6,436 of Antelman, described in 420, it is incorporated into way of reference in full.
But filtering precipitate is to remove excessive source of silver ions metal; Then can be on goods described herein with gained silver colored solutions deposition (by contact and/or non-contact method); Dry (for example, utilizing air then in about 70 ℃ baking oven) obtains discharging the colored materials of silver ion then.
The coloured structure or the particle that discharge silver ion can have any available size.In many examples, the colored materials that discharges silver ion has less than one micron or in the scope of 1 to 500 nanometer or in the scope of 1 to 250 nanometer or in the scope of 1 to 100 nanometer or the average diameter in 5 to 50 nanometer range.
The colored materials 120 that discharges silver ion can be provided with so that cambium layer, labelling, pattern or the like by the contiguous substrate 110 of any available method.In many examples, adhesive phase 130 is a pressure sensitive adhesive layer, and the colored materials 120 of release silver ion is arranged at least a portion of pressure sensitive adhesive layer 130.In certain embodiments, the colored materials 120 that discharges silver ion can deposit by means of contact deposition or noncontact and be provided with.
Suitable noncontact deposition process can not rely on the surface that is coated.Equally, the noncontact precipitation equipment can laterally move along being coated the surface, and applies cross force for basically said surface.With to contact painting method opposite, the noncontact deposition allows identical treatment facility to be used to apply multiple different surface, and need not change preparation or technological parameter.The instance of suitable noncontact deposition process comprises ink jet printing, jet atomization deposition, electrostatic precipitation, differential is joined and mesoscale deposits.Especially suitable noncontact deposition process comprises ink jet printing and jet atomization deposition.
The work of ink jet printing is through the droplet of fluid pattern with control silver-colored colored solutions for example to be sprayed on the adhesive phase 130.The instance of suitable ink jet printing method comprises hot ink-jet, continous inkjet, piezoelectric ink jet, bubble ink-jet, the ink-jet of drop on demand ink jet harmony.The commercially available acquisition of the print head of this printing process is from Hewlett-Packard Corporation, Palo Alto, CA andLexmark International, Lexington, KY (hot ink-jet); Domino PrintingSciences, Cambridge, UK (continous inkjet); With Trident International, Brookfield, CT, Epson, Torrance; CA, Hitachi Data Systems Corporation, Santa Clara, CA, Xaar PLC; Cambridge, UK, Spectra, Lebanon, NH; With Idanit Technologies, Ltd., Rishon Le Zion, Israel (piezoelectric ink jet).The instance of suitable ink jet printing head model comprises NOVA series, such as the NOVA-Q print head and the XJ128 series that can be purchased acquisition from Spectra Inc., such as the XJ128-200 print head that can be purchased acquisition from Xaar PLC.When using the XJ128-200 print head, can be through silver/colored solutions being coated on the adhesive phase 130 with 1.25 kilo hertzs (kHz) and 35 volts of (V) Piezoelectric Driving print heads, printed resolution is per inch 300 * 300 points (dpi).This generation has the drop of about 70 skin liter (pL) nominal volumes.
Ink jet printing also allows on substrate surface 112 and/or adhesive phase 130, to produce silver ion release has color marker 120 and/or figure 120.Equally, silver-colored colored solutions ink jet printing also can be transmitted literal and graphical messages at said lip-deep pattern.In one embodiment, said message can be included in pigment or dyestuff in the silver-colored colored solutions and visually visible through use, when said silver-colored colored solutions basically after the drying, pigment or dyestuff keep concentrating from the teeth outwards or near.In many examples, source of silver ions itself can form the painted of message from the teeth outwards.For example, many chemical compounds that comprise silver like silver nitrate, are transparent in fluid solution, but when drying (or being reduced), become dark brown.This has got rid of the additional coloring agent of needs makes the pattern of ink jet printing visually visible.The instance of suitable message comprises operation instruction, the brand name of Company Logo, goods and is used for the design of aesthetic appearance.
The sedimentary work of jet atomization is through silver-colored colored solutions being sprayed through air injection nozzle or stripping nozzle so that silver-colored colored solutions atomizes to a certain degree.Silver-colored colored solutions after the atomizing concentrates on adhesive phase 130 or the substrate surface 112 then.The instance of suitable jet atomization depositing system comprises commercially available fog-spray nozzle and body, as available from Spraying Systems Co., Wheaton, those of IL.Fog-spray nozzle also can comprise the fan-spray transformation so that scattered to produce oval logo in main jet mist source.Suitable operating condition comprises the volume flow rate with about 5 ml/min (mL/min), the web speed of about 15 feet per minute clocks (about 4.6 meters/minute) and about 23 pounds/inch
2(psi) fan nozzle of the rose setting of (about 159 kPas (kPa)) and about 20psi (about 138kPa) is provided with silver-colored colored solutions is sprayed on the said surface.Fog-spray nozzle produces to have at about 2 microns droplets to about 20 micrometer range interior diameters.
Silver-colored colored solutions as herein described advantageously demonstrates enough low viscosity so that apply with the noncontact deposition.The viscosity that needs depends on the noncontact deposition process of use usually.For example, for ink jet printing, the ink-jet temperature (being generally about 25 ℃ to about 65 ℃) of needs down silver-colored colored solutions advantageously appear and be lower than about 30 centipoises (that is, 30 milli handkerchief-second), or be lower than about 25 centipoises, or be lower than the viscosity of about 20 centipoises.Yet the optimum viscosity characteristic of silver-colored colored solutions will depend primarily on the type of ink-jet temperature and used ink-jet system.Use for piezoelectric ink jet, under about 25 ℃ of temperature to about 65 ℃ of scopes, the appropriate viscosity of silver-colored colored solutions is about 3 to about 30 centipoises, or about 10 to the scope of about 16 centipoises.
The appropriate article that the colored materials 120 of the available release silver ion of biological activity goods 100 representatives is made.In many examples, goods 100 are the binding agent medical product, such as the binding agent wound dressing.The instance of suitable bonding medical product comprises the binding agent wound dressing, and trade name is " TEGADERM " dressing, and it can be from 3M Company, and St.Paul MN) is purchased acquisition.
The body that the substrate 110 of goods 100 limits goods 100 usually is (like (gauze bandage of wound dressing).Optional adhesive phase 130 can be one deck and is arranged on the pressure sensitive adhesive material on the substrate surface 112, so that goods 100 are sticked to another surface, for example, on patient's the skin.Illustrated layer is not in scale.In certain embodiments, colored materials layer 120 can make up so that colored materials is dispersed in the binding agent with adhesive phase 130.
The instance that is suitable for the material of doing substrate 100 comprises fabric, non-woven or nonwoven polymer net; Comprise use blowing microfibre technology, braiding, polymeric film, aqueous colloidal, foam, metal forming, paper, gauze, natural or synthetic fibers, cotton, artificial silk, Pilus Caprae seu Ovis, Fructus Cannabis, Corchorus olitorius L., nylon, polyester, gather acetate, polyacrylate, alginate, ethylene-propylene-diene rubber, natural rubber, polyester, polyisobutylene, polyolefin (as; Polypropylene-polyethylene, ethylene propylene copolymer and ethylene-butylene copolymer), polyurethane (comprising polyurethane foam), vinyl comprises polrvinyl chloride and ethene-vinyl acetate, polyamide, polystyrene, fibre glass, ceramic fibre, elastomer, thermoplastic polymer, and their combination.These materials can be used as the backing substrate in the multiple conventional medical product.
In many examples, adhesive phase 130 is contact adhesive (PSA).The instance that is suitable for the material of making adhesive phase 130 comprises the PSA based on acrylic ester, polyurethane, organosilicon, rubber-based adhesive (comprising natural rubber, polyisoprene, polyisobutylene and butyl rubber), and their combination.The instance of suitable acrylic ester comprises the polymer of alkyl acrylate monomer, such as methyl methacrylate, EMA, the positive butyl ester of methacrylate, acrylic acid methyl ester., ethyl acrylate, n-butyl acrylate, Isooctyl acrylate monomer, acrylic acid ester in the different ninth of the ten Heavenly Stems, 2-ethyl-ethylhexyl acrylate, decyl acrylate, dodecyl acrylic ester, n-butyl acrylate, Hexyl 2-propenoate and their combination.
In certain embodiments, the material that is used for adhesive phase 130 comprises organic silicon-based adhesive, and it shows several kinds of useful character, is superior to used traditional PSA in the wound care application.For example, the organosilicon based adhesive can be mixed with provides the good skin attachment characteristic, excellent stickiness is provided and skin is provided and the temperature of wound site is closed release.The organosilicon based adhesive can reaction forms as two parts system through organopolysiloxane gel and resin, a part of obstruction system inhibition premature reaction, or even as the heat fusing system.The instance of suitable organosilicon based adhesive comprises the polydiorganosiloxanepolyurea based adhesive; The city is sold by Dow Corning Corp., Midland, the binding agent of MI with the biomedical grade adhesive of trade name " SILASTIC 7-6860 "; Disclosed binding agent in people's such as Sherman the United States Patent (USP) 6,407,195, it incorporates this paper by reference into; And their combination.
In certain embodiments, source of silver ions can be reduced with method of reducing known in the art before or after being applied to silver-colored colored solutions on the goods 100.For example, through using Reducing agent (for example, three (dimethylamino) borine, sodium borohydride, potassium borohydride or ammonium borohydride), electron beam (electron beam) processing or ultraviolet (UV) light to implement reduction.
The nonferrous layer 120 that discharges silver ion can be dry before or after reduction step.The drying that is coated goods 100 can use any method that is suitable for dry aqueous coating to realize.Available drying means will not damage coating or significantly destroy the orientation that the coating of giving in coating or the application discharges the nonferrous layer 120 of silver ion.
As stated, in many examples, source of silver ions 122 provides the painted of message on the goods 100.For example, many chemical compounds that comprise silver like silver nitrate, are transparent in fluid solution, but when drying (or being reduced), become dark brown.After silver ion discharged from goods 100, the painted of message, labelling and/or pattern faded.Therefore, user can confirm that silver ion releasing articles no longer discharges the time of silver ion (being commonly referred to " life latter stage " indicator).
Instance
The present invention should not be considered to only limit to instantiation as herein described.On the contrary, should be understood that to cover in the appended claims the various aspects of the present invention that clearly propose.After those skilled in the art in the invention read this description, be applicable to that various modification of the present invention, equivalent method and various structure will become obvious for them.
It is as used herein,
" PET " be meant have about 102 microns (0.004 inch) thickness gather (ethylene glycol terephthalate) thin film, can derive from Mitsubishi Polyester Corp., Tokyo, Japan;
" TEGADERM " is meant a kind of binding agent wound dressing, by 3M Company, and St.Paul, MN makes;
" paper TEGADERM " is meant a kind of paper binding agent wound dressing, by 3MCompany, and St.Paul, MN makes;
" PVA film " be meant a kind of have about 40 microns (0.0016 inch) thickness gather (vinyl alcohol) film, can derive from Mitsui Plastics Inc., White Plains, NY;
" TIPS film " is meant a kind of microporous polypropylene membrane, like United States Patent (USP) 4,726, and 989 and 5,120,594 said preparations;
" MPS film " is meant a kind of polypropylene nonwoven, like United States Patent (USP) 6,110, and preparation described in 588;
" SPUNBOND " is meant spunbond polypropylene, can derive from Hanes Companies, Inc., and Conover, NC);
" GAUZE " is meant cotton nonwoven scrim, can derive from American Fiber &Finishing, Inc., Albemarle, NC;
" FOAM " is meant a kind of non-sticky foam wound dressing (it is believed that and be the polyurethane open celled foam), obtains from 3M Company, St.Paul, MN with production code member 90-601;
" PP NONWOVEN " is meant a kind of polypropylene blow moulding microfibre non-woven material.
The inhibition zone test
The antimicrobial acivity that comprises the substrate of the colored materials (biological activity goods) that discharges silver ion uses the inhibition zone to test and estimates.Preparation staphylococcus aureus (A.T.C.C.25923) solution, concentration is every milliliter 1 * 10 in phosphate buffered saline (PBS) (PBS)
8CFU (CFU) uses 0.5McFarland reduced turbidity standard.The preparation of lawn is through aseptic cotton applicator being immersed in the said solution, smearing the dull and stereotyped desiccated surface of trypticase soy agar along three different directions then.Three 7 mm dia dishes of each sample are used the PBS moistening, are placed on the flat board then, and firmly press to agar to guarantee to contact agar with aseptic nipper.Flat board is placed in the refrigerator three hours in 4 ℃, and cultivated 24 hours in 36 ℃, during this period of time after, the dull and stereotyped inhibition of going up staphylococcus aureus growth of inspection.Confirming of main inhibition zone through measuring on the agar plate below the dish that the wherein growth of staphylococcus aureus is suppressed (main inhibition zone) basically fully the diameter with the peripheral region.Confirming of inferior inhibition zone through measuring on the agar plate diameter that crosses disk area that the wherein growth of staphylococcus aureus is suppressed by part.Be recorded as each regional diameter (unit for millimeter) below the value of main and secondary inhibition zone, comprise the zone below the 7mm diameter sample dish.
Ink jet printing
The ink jet printing of substrate uses model to carry out as the piezoelectricity print head of XJ128-200, and it is by Xaar PLC, Cambridge, and United Kingdom makes, and has nominal droplet size that 70 skins rise and the printed resolution of 300 * 300dpi (dots per inch).Said print head drives under 1250Hz and 35V.The printed resolution of 300 * 300dpi provides 90,000 (300 * 300) per square inch under 100% substrate surface coverage rate.Drop through depositing still less per square inch can obtain littler substrate surface coverage rate.Therefore, deposit 27,000 per square inch and can produce 30% substrate surface coverage rate.
Adhesive force is measured
The bonding strength of the adhesive article for preparing in the instance is used to obtain from Thwing-Albert Instrument Co. according to ASTM D3330, Philadelphia, and the Thwing-Albert cupping machine of PA is measured.Test surfaces is by #302 AISI stainless steel annealing surface composition, with isopropyl alcohol that waits umber by weight and heptane mixture cleaning.Sample stretches with 180 ° of angles with the chuck speed of 300 millimeters of per minutes and 125 millimeters gauge length.The bonding strength that writes down in the instance is six meansigma methodss of measuring.
Preparation property instance 1
The preparation of silver colored solutions
The mixture of the colored compound of chemical formula V (1.0g), deionized water (4.0g) and ethanolamine (0.16g) stirs about two hours together.In this agitating solution, add the solution that makes through combination deionized water (4.0g), silver nitrate (0.4g) and ethanolamine (0.53g).The gained mixture stirs and obtained silver-colored colored solutions in about 30 minutes.
Instance 1
The preparation of PET biological activity goods
Use recess coating bar to be coated on the PET thin slice the silver-colored colored solutions of preparation property instance 1.The thickness of wet coating is about 8 microns (0.0003 inches).Coating uses hot-air syringe dry.Then the thin slice that is coated was placed in the seal glass wide mouthed bottle that contains borine five minutes, it is exposed in three (dimethylamino) borine steam.Recording main inhibition zone is 12 millimeters.
Instance 2-9
Prepare the biological activity goods through ink jet printing,
The silver-colored colored solutions of a preparation property instance 1 is by weight mixed with three parts of deionized waters by weight.Substrate surface coverage rate with 100% with this mixture ink jet printing in table 1 in the listed substrate.The dish of three every kind of printed substrates, each has seven millimeters diameter, uses above-mentioned inhibition zone test to estimate.Data provide in table 1.In table 1, " ZOI " representes the inhibition zone.The bonding strength of ink jet printing TEGADERM film is estimated as stated, and finds that it is every centimetre of 160.7+/-11.5 gram (per inch 14.40+/-1.03 ounce).
The inhibition zone data of table 1. instance 2-9
| Instance | Substrate | Main ZOI (mm) | Inferior ZOI (mm) |
| 2 | The TEGADERM film | 7 | 10 |
| 3 | GAUZE | 11 | 12 |
| 4 | The PVA film | 7 | 11 |
| 5 | The TIPS film | 10 | 0 |
| 6 | The MPS film | 0 | 9 |
| 7 | SPUNBOND | 11 | 13 |
| 8 | FOAM | 9 | 12 |
| 9 | PP?NONWOVEN | 7 | 9 |
Instance 10
Biological activity goods with time dependence
The silver-colored colored solutions of a preparation property instance 1 is by weight mixed with three parts of deionized waters by weight.One milliliter of this mixture is applied on 51 millimeters * 51 millimeters (2 inches * 2 inches) gauze samples.Then gauze in convection oven in 80 ℃ of dryings ten minutes.Then dried gauze was placed in the seal glass wide mouthed bottle that contains borine ten minutes, it is exposed in three (dimethylamino) borine steam.The dish of gauze after three processing, each has seven millimeters diameter, uses inhibition zone test in 24 hours to estimate.After writing down the result, each dish is taken out (under aseptic condition) from agar plate, place on second agar plate the reactive golden yellow color staphylococcus bacterium colony of making a living on it and having then.With this second dull and stereotyped cultivation 24 hours, then write down the inhibition zone then.Each dish is taken out (under aseptic condition) from second agar plate, place on the 3rd agar plate reactive golden yellow color staphylococcus bacterium colony of making a living on it and having then.With this 3rd dull and stereotyped cultivation 24 hours, then write down the inhibition zone then.After first dull and stereotyped last the first day, after second dull and stereotyped last the second day and the 3rd inhibition zone (the inhibition zone data of time dependence) after dull and stereotyped last the 3rd day is given in the table 2, and the note work is the 1st day, the 2nd day and the 3rd day respectively.
The time dependence inhibition zone data of table 2. instance 10
| Natural law | Main ZOI (mm) | Inferior ZOI (mm) |
| The 1st day | 11 | 12 |
| The 2nd day | 8 | 9 |
| The 3rd day | 0 | 8 |
Instance 11-12
Through spraying preparation biological activity goods
The silver-colored colored solutions of a preparation property instance 1 is by weight mixed with two parts of deionized waters by weight.Use aerosol apparatus/rose that this mixture is sprayed on paper TEGADERM net (instance 11) and the PET net (instance 12), said aerosol apparatus/rose produces has about two microns droplets to about 20 micrometer range interior diameters.Mist flow is 20 milliliters of about per minutes, and web speed is 4.6 meters of about per minutes (about 15 feet).The film that is coated in convection oven in about 150 ℃ of dryings ten minutes.Then the diaphragm that is coated was placed in the seal glass wide mouthed bottle that contains borine five minutes, it is exposed in three (dimethylamino) borine steam.The antimicrobial acivity of each coating film uses above-mentioned inhibition zone test to estimate.In instance 11, paper TEGADERM demonstrates 10 millimeters main inhibition zone and 12 millimeters inferior inhibition zone.In instance 12, PET demonstrates 11 millimeters main inhibition zone and 13 millimeters inferior inhibition zone.
The bonding strength of the paper TEGADERM film of ink jet printing is estimated as stated, and finds that it is every centimetre of 131.6+/-10.4 gram (per inch 11.79+/-0.93 ounce).
Comparative example 1
The inhibition zone data of TEGADERM
The antimicrobial acivity of the TEGADERM dish (not handling with silver-colored colored solutions) of three seven mm dias uses above-mentioned inhibition zone to test and estimates.The main and secondary inhibition zone is zero.The bonding strength of this TEGADERM film (with silver-colored colored solutions handle) is estimated as stated, and finds that it is every centimetre of 160.5+/-15.7 grams (per inch 11.79+/-0.93 ounce).
Claims (20)
1. wound dressing that comprises the biological activity goods, said biological activity goods comprise:
Substrate, it has substrate surface; With
Discharge the colored materials of silver ion, its contiguous said substrate surface setting, the colored materials of said release silver ion comprises colored compound and source of silver ions, the colored materials of wherein said release silver ion can be represented with in the following universal architecture at least one:
For structural formula (I), each R
2Be independently selected from the group of forming by following: electron-donating group, electron withdraw group and electric neutrality group; R
3Be selected from the group of being made up of following: replace and unsubstituted hetero-aromatic ring and replacement and unsubstituted heterocycle, these rings pass through R
3Intra-annular nitrogen-atoms is connected on the triazine group, and M
+Be the silver metal cation;
For structural formula (II), each R
2Be independently selected from the group of forming by following: electron-donating group, electron withdraw group and electric neutrality group; R
3Be selected from the group of being made up of following: replace and unsubstituted hetero-aromatic ring and replacement and unsubstituted heterocycle, these rings pass through R
3Intra-annular nitrogen-atoms is connected on the triazine group, and M
+Be the silver metal cation;
For structural formula (III), M
+Be silver metal cation, X
-Be counter ion counterionsl gegenions; With
For structural formula (IV), M
+Be the silver metal cation.
2. wound dressing according to claim 1, wherein said substrate comprises non-woven material.
3. wound dressing according to claim 1, wherein said substrate comprises weaving material.
4. wound dressing according to claim 1; Wherein said substrate also comprises the contact adhesive between the colored materials that is arranged on said substrate and said release silver ion, and the colored materials of said release silver ion is arranged at least a portion of said contact adhesive.
5. wound dressing according to claim 1, the colored materials of wherein said release silver ion forms labelling.
6. wound dressing according to claim 1, the colored materials of wherein said release silver ion forms pattern.
7. wound dressing according to claim 4 also comprises the release liner that is arranged on the said pressure sensitive adhesive layer.
8. wound dressing according to claim 1, the colored materials of wherein said release silver ion is arranged in the said substrate.
9. wound dressing according to claim 1, wherein said source of silver ions comprises silver or silver oxide.
10. wound dressing according to claim 1, wherein said source of silver ions have the average diameter in 1 to 500 nanometer range.
11. a method that forms the described wound dressing of claim 1 comprises:
Substrate with substrate surface is provided;
Silver salt and colored compound are combined to form aqueous silver colored solutions in aqueous solution;
With the contiguous said substrate surface setting of said silver-colored colored solutions, the substrate that is coated with formation; And
Except that anhydrating, discharge the nonferrous layer of silver ion from the said substrate that is coated with formation.
12. method according to claim 11 wherein saidly provides step to comprise the substrate with substrate surface to be provided and to be arranged on the contact adhesive on the said substrate surface; And the wherein said step that is provided with comprises said silver-colored colored solutions is arranged on the said contact adhesive, the substrate that is coated with formation.
13. method according to claim 11, the wherein said step that is provided with comprise with the noncontact deposition process the contiguous said substrate surface setting of said silver-colored colored solutions, the substrate that is coated with formation.
14. method according to claim 11, the wherein said step that is provided with comprises the said silver-colored colored solutions of contiguous said substrate surface ink jet printing, the substrate that is coated with formation.
15. method according to claim 11 also comprises and reduces the colored materials layer of said release silver ion.
16. method according to claim 11, the wherein said step that is provided with comprises that contiguous said substrate surface is provided with said silver-colored colored solutions, so that contiguous said substrate forms labelling or pattern.
17. method according to claim 12, the wherein said step that is provided with comprise said silver-colored colored solutions are arranged on the said contact adhesive, so that on said contact adhesive, form labelling or pattern.
18. method according to claim 11 also comprises the nonferrous layer contact with water that makes said release silver ion, so that discharge silver ion from the nonferrous layer of said release silver ion.
19. method according to claim 11, wherein said combination step comprise silver nitrate and colored compound are made up in aqueous solution, to form aqueous silver colored solutions.
20. method according to claim 12 also comprises release liner is applied on the said contact adhesive.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/275,075 US7807661B2 (en) | 2005-12-08 | 2005-12-08 | Silver ion releasing articles and methods of manufacture |
| US11/275,075 | 2005-12-08 | ||
| PCT/US2006/046387 WO2007067535A1 (en) | 2005-12-08 | 2006-12-05 | Silver ion releasing articles and methods of manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101325980A CN101325980A (en) | 2008-12-17 |
| CN101325980B true CN101325980B (en) | 2012-10-03 |
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ID=38123219
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200680045936XA Expired - Fee Related CN101325980B (en) | 2005-12-08 | 2006-12-05 | Silver ion releasing articles and methods of manufacture |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US7807661B2 (en) |
| EP (1) | EP1962915B1 (en) |
| JP (1) | JP2009518124A (en) |
| CN (1) | CN101325980B (en) |
| BR (1) | BRPI0619511A2 (en) |
| WO (1) | WO2007067535A1 (en) |
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| US7807661B2 (en) | 2005-12-08 | 2010-10-05 | 3M Innovative Properties Company | Silver ion releasing articles and methods of manufacture |
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| US7824732B2 (en) * | 2005-12-28 | 2010-11-02 | 3M Innovative Properties Company | Encapsulated chromonic particles |
| US20080114177A1 (en) * | 2006-11-15 | 2008-05-15 | 3M Innovative Properties Company | Method for preparing fluorinated benzotriazole compounds |
| WO2009097508A2 (en) * | 2008-01-30 | 2009-08-06 | Mcanulty, Jonathan | Methods and compositions for wound healing |
| GB0906056D0 (en) | 2009-04-08 | 2009-05-20 | Brightwake Ltd | Absorbent wound dressing for wrapping around jointed limbs |
| US8641967B2 (en) | 2011-02-23 | 2014-02-04 | Applied Silver, Inc. | Anti-microbial device |
| AU2014260033B2 (en) | 2013-05-02 | 2019-06-27 | Medical Technology Research Inc. | Antimicrobial compositions and methods of making the same |
| US11618696B2 (en) | 2013-08-15 | 2023-04-04 | Applied Silver, Inc. | Antimicrobial batch dilution system |
| US10640403B2 (en) | 2013-08-15 | 2020-05-05 | Applied Silver, Inc. | Antimicrobial batch dilution system |
| US9937156B2 (en) | 2013-10-16 | 2018-04-10 | The Board Of Regents Of The University Of Texas System | Modulation of MRTF-A activity in pathologic fibrosis and wound healing |
| US9689106B2 (en) | 2013-12-06 | 2017-06-27 | Applied Silver, Inc. | Antimicrobial fabric application system |
| WO2016040695A1 (en) | 2014-09-10 | 2016-03-17 | C.R. Bard, Inc. | Protective dressing for skin-placed medical device |
| EP2995324A1 (en) | 2014-09-11 | 2016-03-16 | Mölnlycke Health Care AB | Medical dressing |
| EP2995287A1 (en) | 2014-09-11 | 2016-03-16 | Mölnlycke Health Care AB | Medical dressing |
| EP3201182A4 (en) | 2014-10-01 | 2018-06-13 | Medical Technology Research Inc. | Antimicrobial compounds, methods of making the same and articles comprising them |
| US20170050870A1 (en) | 2015-08-21 | 2017-02-23 | Applied Silver, Inc. | Systems And Processes For Treating Textiles With An Antimicrobial Agent |
| US10760207B2 (en) | 2017-03-01 | 2020-09-01 | Applied Silver, Inc. | Systems and processes for treating textiles with an antimicrobial agent |
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- 2006-12-05 JP JP2008544436A patent/JP2009518124A/en active Pending
- 2006-12-05 WO PCT/US2006/046387 patent/WO2007067535A1/en active Application Filing
- 2006-12-05 EP EP06838999.8A patent/EP1962915B1/en not_active Not-in-force
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Also Published As
| Publication number | Publication date |
|---|---|
| US7807661B2 (en) | 2010-10-05 |
| EP1962915A1 (en) | 2008-09-03 |
| US20070134301A1 (en) | 2007-06-14 |
| EP1962915A4 (en) | 2012-06-13 |
| EP1962915B1 (en) | 2013-08-14 |
| BRPI0619511A2 (en) | 2011-10-04 |
| CN101325980A (en) | 2008-12-17 |
| JP2009518124A (en) | 2009-05-07 |
| WO2007067535A1 (en) | 2007-06-14 |
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